: Geochemical reaction path modeling is useful for rapidly assessing the extent of water-aqueous-gas interactions both in natural systems and in industrial processes. Modeling of some systems, such as those at low temperature with relatively high hydrologic flow rates, or those perturbed by the subsurface injection of industrial waste such as CO2 or H2S, must account for the relatively slow kinetics of mineral-gas-water interactions. We have therefore compiled parameters conforming to a general Arrhenius-type rate equation, for over 70 minerals, including phases from all the major classes of silicates, most carbonates, and many other non-silicates. These data have been added to a computer code that simulates an infinitely well-stirred batch reactor, allowing computation of mass transfer as a function of time. Actual equilibration rates are expected to be much slower than those predicted by the selected computer code, primarily because actual geochemical processes commonly involve flow through porous or fractured media, wherein the development of concentration gradients in the aqueous phase near mineral surfaces, which results in decreased absolute chemical affinity and slower reaction rates. Further differences between observed and computed reaction rates may occur because of variables beyond the scope of most geochemical simulators, such as variation in grain size, aquifer heterogeneity, preferred fluid flow paths, primary and secondary mineral coatings, and secondary minerals that may lead to decreased porosity and clogged pore throats.

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A Compilation of Rate Parameters of Water-Mineral Interaction Kinetics for Application to Geochemical Modeling

https://www.metakaolin.ru/Documents/CementandConcreteResearch.pdf

A review: The comparison between alkali-activated slag (Si + Ca) and metakaolin (Si + Al) cements

The current widespread use of calcium silicate or aluminate hydrate binder systems in the construction industry finds its roots in the Antique world where mixtures of calcined lime and finely ground reactive (alumino-)silicate materials were pioneered and developed as competent inorganic binders. Architectural remains of the Minoan civilization (2000-1500 BC) on Crete have shown evidence of the combined use of slaked lime and additions of finely ground potsherds to produce stronger and more durable lime mortars suitable for water-proof renderings in baths, cisterns and aqueducts (Spence and Cook 1983). It is not clear when and where mortar technology evolved to incorporate volcanic pumice and ashes as a functional supplement. A plausible site would be the Akrotiri settlement at Santorin (Greece), where archeological indications of strong ties with the Minoan culture were found and large quantities of suitable highly siliceous volcanic ash were present. This so-called Santorin earth has been used as a pozzolan in the Eastern Mediterranean until recently (Kitsopoulos and Dunham 1996). Evidence of the deliberate use of this and other volcanic materials by the ancient Greeks dates back to at least 500-400 BC, as uncovered at the ancient city of Kamiros, Rhodes (Efstathiadis 1978; Idorn 1997). In the subsequent centuries the technological knowledge was spread to the mainland (Papayianni and Stefanidou 2007) and was eventually adopted and improved by the Romans (Mehta 1987). The Roman alternatives for Santorin earth were volcanic pumices or tuff found in neighboring territories, the most famous ones found in Pozzuoli (Naples), hence the name pozzolan, and in Segni (Latium). Preference was given to natural pozzolan sources, but crushed ceramic waste was frequently used when natural deposits were not locally available. The exceptional lifetime and preservation condition of some of the most famous Roman buildings such as the Pantheon or the Pont du …

Supplementary Cementitious Materials

The rates of mineral dissolution contribute to processes controlling soil fertility, porosity in aquifers and oil reservoirs, transport and sequestration of contaminants and CO2, cycling of metals and formation of ore deposits, and many other geochemical characteristics and phenomena. For example, the weathering rates of Caand Mg-silicates influence the concentrations of CO2 in the atmosphere over 105–106 y timescales, impacting the global carbon cycle. Mineral dissolution thus influences the chemical and physical nature of our landscape as well as the quality and quantity of potable water and fertile soil available to sustain ecosystems. The rates of mineral dissolution (Fig. 5.1) determine the lifetimes of minerals in soil environments. Especially since the 1970s, researchers have focused on measurement of mineral dissolution rates in order to promote quantitative prediction of the evolution of our environment (Stumm, 1997). In this chapter, we discuss many of the concepts and models used to predict mineral dissolution rates for oxide, carbonate, and silicate minerals.

Kinetics of Mineral Dissolution

A physico-chemical basis for novel cementitious binders

Introduction: Dissolution and precipitation of feldspar is an important reaction in many environmental systems, as plagioclase feldspar is the most common mineral in the crust. However, the mechanism of dissolution of feldspar has remained in dispute despite twenty or more years of analysis of feldspar dissolution. We are pursuing an approach toward better understanding of feldspar dissolution by investigating reactivity of aluminosilicate glasses of variable composition. In particular, to investigate the effects of Al/Si ratio on plagioclase dissolution without complications of varying Na/Ca content or exsolution, three glasses with varying Al/Si ratio (albite, jadeite, nepheline) were synthesized. Glass powders were then prepared and dissolved at various values of pH in batch reactors under ambient conditions. Solution chemistry was analyzed by inductively coupled plasma -optical emission spectroscopy or -mass spectrometry. In addition, alteration of the glass surface was investigated using Xray photoelectron spectroscopy, secondary ion mass spectrometry, and Fourier transform infrared spectroscopy. Dissolution results: Many similarities in dissolution behavior between plagioclase crystals and this suite of glasses were observed: 1) dissolution was slowest at near-neutral pH and increased under acid and basic conditions, 2) dissolution rate at all pH values increased with increasing Al/Si ratio, 3) the pH dependence of dissolution was higher for the phase with Al/Si = 1 than the phase with Al/Si = 0.3, 4) after acid leaching, the extent of Al-depletion of the altered surface increased with increasing bulk Al/Si ratio from Al/Si = 0.3 (albite) to 0.5 (jadeite), but then decreased in nepheline (Al/Si = 1.0), which dissolved stoichiometrically with respect to Al, and 5) little to no Al depletion of the surface of any glass occurred at pH > 7. However, in contrast with some observations for plagioclase dissolution, log(rate) increased almost linearly with Al content, and n, the slope of the log(rate)pH curve at low pH, varied smoothly from albite to jadeite to nepheline (n = 0.3, 0.6, 1.0 respectively). At high pH, the slope of this curve, m, did not differ between glasses (m = -0.4 + 0.1). Mechanistic interpretation: These results are consistent with an identical mechanism controlling dissolution of nepheline, albite, and jadeite glass, although no Si-rich layer can develop on nepheline because of the lack of Si-O-Si linkages. Such a conclusion is consistent with a transition state for these aluminosilicates at high pH consisting of a deprotonated Q3 hydroxyl group (where Qv refers to an x atom in a tetrahedral site with v bridging oxygens) or a five-coordinate Si site after nucleophilic attack by OH, and, at low pH, a protonated Q4OQ4. At low pH, we infer that Q4OQ4 Al linkages are ratelimiting because they are presumed to hydrolyze more slowly than Qv OQw Si (v,w < 3). According to this model, dissolution rate increases from albite to jadeite to nepheline because hydrolysis of Al-O-Si linkages becomes more energetically favorable as the number of Al atoms per Si tetrahedral increases, a phenomenon documented by geometry optimizations using ab initio methods (for example, Figure 1). However, a model wherein Q4OQ4 Si linkages are faster to hydrolyze than lower connectivity linkages between Si atoms (Qv OQw , v,w < 3) may also explain aspects of this data.

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L. Criscenti

Papers

Role of Polymerization in the Dissolution of Nepheline, Jadeite, and Albite Glasses: Toward Better Models for Aluminosilicate Dissolution